Issue 19, 2023

Synthesis and reactivity of a uranium(iv) complex supported by a monoanionic nitrogen–phosphorus ligand

Abstract

A monoanionic nitrogen–phosphorus ligand (CH3)2NCH2CH2NHPiPr2 (L3) was designed and the corresponding U(IV) chloride complex {[(CH3)2NCH2CH2NPiPr2]2UCl2} (1) and U(IV) iodide complex {[(CH3)2NCH2CH2NPiPr2]2UI2} (2) were readily synthesized. Complexes 1 and 2 were fully characterized and the reactivity of complex 1 was further investigated. Complex 3 {[(CH3)2NCH2CH2NPiPr2]2U(C12H8)} with a uranium cyclopentadiene unit was constructed by the reaction of 1 with 2,2′-dilithiobiphenyl, which is a rare example of a homoleptic metallafluorene containing an actinide element. In addition, a U(IV) bi-alkyl complex {[(CH3)2NCH2CH2NPiPr2]2U[o-N(CH3)(CH2)C6H4CH2]} (4) was isolated by the reaction of complex 1 with two equivalents of o-N(CH3)2C6H4CH2K. Moreover, the reactivity of 1 with a series of transition metal precursors was also investigated, from which heterometallic clusters {[(CH3)2NCH2CH2NPiPr2]2UCl2(μ-Cl)RuCl}2 (5), {[(CH3)2NCH2CH2NPiPr2]2UCl2Rh(μ-Cl)}2 (6) and {[(CH3)2NCH2CH2NPiPr2]2UCl2Ir(μ-Cl)}2 (7) were isolated. The U–Rh and U–Ir single bonds were observed in complexes 6 and 7, respectively. This study further confirms that the nitrogen–phosphorus ligand is an effective platform for the construction of species with U–M bonds.

Graphical abstract: Synthesis and reactivity of a uranium(iv) complex supported by a monoanionic nitrogen–phosphorus ligand

Supplementary files

Article information

Article type
Research Article
Submitted
25 jul 2023
Accepted
17 aug 2023
First published
17 aug 2023

Inorg. Chem. Front., 2023,10, 5622-5633

Synthesis and reactivity of a uranium(IV) complex supported by a monoanionic nitrogen–phosphorus ligand

K. Li, J. He, Y. Zhao and C. Zhu, Inorg. Chem. Front., 2023, 10, 5622 DOI: 10.1039/D3QI01447A

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